Azo dyestuffs containing chromium in complex union



Patented Sept. 30, 1941 UNITE-D 2,257,1"6'5 Fries ,AZO DYES'IUFFS CONTAINING CHROMIUM "."IN'COIWPLEX UNION Ernst Fellmer, Leverkusen I. G'.-Werk, Germany,

assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware N Drawing. Application March 16, 1940, Serial In Germany November 25, 1933 4 Claims. Cl. 260-145) The presentinvention' relates to new 'azodyestuffs containing chromium in complex union, more particularly it relates to chromium complex .compoundsof azodyestuifs, which may be represented by the following formula:

In this formula R stands for a radical of the I naphthalene series, R1 and R2 stand for radicals l per one chromium atom.

- My new dyestuffs are'obtainable bystarting with a monoazodyestuff of the general formula:

wherein X stands for hydroxyl, alkoxy or the carboxylic acid group R and R3 means the same as above, coupling this monoazodyestuif with a diazo' compound suitable for preparing azodyestuffs, if desired, coupling with a further diazo compound suitable for preparing azodyestuffs, and transforming the dyestuffs thus obtained into the chromium complex compounds of the cor-' responding o-hydroxy or o-carboxy azodyestuffs. This transformation into the chromium complex compounds may be performed according to known methods either in the final dyestufis or man intermediate stage of the dyestuff preparation either in an acid, neutral or an alkaline medium and, if necessary, under pressure. It is selfunderstood that if as starting compounds such azodyestuffs of the above'identified second formula are used, in which X stands for alkoxy, the conditions of working must be chosen in such a way that the alkoxy group is split up in the manufacture of the chromium complex compounds. As agents yielding chromium may be used e. g; chromium sulfate, chromium acetate,

chromium formate, chromium fluoride. By the variations possible in the formation of the chromium complex compounds, products may be obtained which differ somewhat in the shades or in the fastness to acid or to alkalies.

in such a way that the chromium complex compounds finally formed contain at most one nitro In preparing the dyestuffs the components are chosen isolated in the'usual manner.

, The new chromium containing dyestuffs --are inform of their alkali metal salts dark watersoluble powders which dye leather even grey-to black shades of good fastness to light and washing; these shades may vary from a pure black to it black shades showing certain tinges. The dyestuffs are in general suitable fordyeing the different kinds of leather such as chromium and vegetable tanned leather; they proved to be especially valuable for dyeing glac leather yielding thereon fine black shades of excellentfastness to Washing which is particularly important sincethis leather is used for makinggloves.

This application is a continuation-impart of my copending application Ser. No. 193,854, filed-4th March, 1938 now patentNo. 2,200,445,- issued May 19, 1940.

The invention is illustrated by the following examples Without being restricted thereto, the parts being by Weight:

Example 1 The sodium hydroxide alkaline solution prepared from 11 parts of 1.3-di'hydroxybenzen'e is coupled with the diazo compound prepared from 28.4 parts of G-nitro-1'amino 2-hydroxynaplithalene--sulfonic acid. The monoaz'odyestuff salted out and isolated 15' then coupled in sodiumhydroxide alkaline, concentrate solution with the diazo compound prepared from 14.3partsof 4- chloro-Zamino-l-hydroxybenzene and, when the coupling is complete, salted out and separated. In order to transform the dyestuff into'the double metal complex compound it is boiled for several hours with an aqueous chromium sulfate solution acid to litmus corresponding to 18.7 parts of CrzOa, made alkaline and clarified and finally The dyestuff which corresponds in its free state, i. e. in the form of the free acid, to the following formula:

dyes leather grey to black shades.

Example 2 lated by acidifying the solution and adding salt.

Thedyestuff is then transformed into its chromium complex compound by refluxing for several hours with aqueous chromium sulfate solution corresponding to 10 parts of C1'2O3. The chr0- mium lake is then coupled in a soda-alkaline medium withthe 'diazo compound prepared from freeacid, to the following formula:

22.3 parts of naphthionic acid and isolated from acid medium. The dyestufi having inits free state, i. e. in the form of the free acid, the

dyes leather grey to greyish-black shades.

Example 3 The diazo compound prepared from 23.9 parts of 1amino-2naphthol-l-sulfunic acid is coupled in sodium hydroxide alkaline solution with 11 parts of reso-rcinol, and the monoazodyestuff is aisolated by acidifying the solution and adding salt. This monoazodyestufi is stirred into water and is coupled in the presence of caustic soda lye with the diazo compound prepared from 15.4 parts of 4-'nitro-2-aminophenol. The disazodye- "stuff obtained is salted out from acid medium, filtered off and-in order to convert it into the double chromium complex compoundboiled for several hours with reflux or heated in the autoclave to 110 C. with an aqueous chromium sulfate solution corresponding to 16.5 parts of CrzOs' at weakly acid reactiornthen made alkaline and clarified still hot and finally isolated and dried in the usual manner. The dyestuff corresponds in the free state, i. e. in the form of the Further examples illustrating the invention HOaS I It dyes leather grey to black shades:

7 ,arestated in the following table:

2,257,165 f f T In the pr-eparation of the dyestuffs 6, 7, 8, l0 and 16 of the above table the formation of the chromium complex compound has taken place after the first coupling.

I claim:

1. Azodyestufis containing chromium in complex union of the general formula:

wherein R stands for a radical of the naphthalene series, R1 and R2 stand for radicals of diazotization compounds suitable for producing azodyestuffs, R3 stands for a member of the group consisting of hydrogen, hydroxyl, alkyl, halogen, COOH and SOaH, :nstands for a member of the group consisting of the hydroxy and the carboxylic acid group, and n stands'for one of the values 1 and 0, which metal complex dyestuffs contain in the radicals R, R1 and R2 together at most one nitro-group per one chromium atom, being in the form of their alkali metal salts dark watersoluble powders dyeing leather fast grey to black shades.

2. Azodyestufis containing chromium in complex union of the general formula:

R I OH chron1ium I J X OH r 1 wherein R stands for a radical of the naphthalene series, R1 stands for a radical of a diazotization component suitable for producing azodyestuffs, R3 stands for a member of the group consisting of hydrogen, hydroxyl, alkyl, halogen, COOH and SOaI-I, and X stands for a member of the group consisting of the hydroxy and the carboxylic acid group, which metal complex sullonic acid.

Diazo component bearing the First diazo component Second diazo Shades on glac lake-forming group (R) Azo component (R1) component (R2) Metal leather LZ-B IIiJJODSPhthOIA-SUHOIHC Resorcinol 4-chloro-2-aminophenol Chromium twice Bluish black.

Do do 4-chloro2-a1m'nophenol- Blue-black. fi-sulfom'c acid.

Do do 4-nitro-2-aminophenol-6- Slightly greenish sulfonic acid. black. Do do 4.6-d1initro-2-aminophe Black.

no ni-chloraniline Violettish black. Dehydrothiotoluidine Greem'sh black.

sulionic acid (obtained by sulfonation) p-nitraniline. -.do- Black. Aminoazobenzene suldo Do. ionic acid. 6-mtro-l.2-aminonaphthol-4- p-chloraniline "do Brownish black.

sulfonic acid.

Do 2-naphthylamine-6-suldo Black.

ionic acid. Do- 4 aminodiphenylamine do Olivish black.

sull'onic acid. Do 4-aminodiphenylether-2- d0 Do.

sull'onic acid. Do 4-chloro-2-aminophenol. 2-nitraniline-4- C h r o m l u In Greenish black.

sulionic acid Do 4-nitro-2-aminophenol Do. Do 5-m'tro-2-aminophenol. d Violettish black. 1.2-aminonaphthol-4-sulfonic 4-nitro-L3-diaminoben- Chromium Black.

acid. zone.

, Do 5-nitro-2-aminophenol--- Cth r o m i u m Bluish black.

W166. Do do do 2 toluidine 5 l d0 Black.

sulfonic acid.

D0 do 4-chloro-2-aminophenoldo do Black-blue.

fi-sulfonic acid.

D0 do 6-chloro-2-aminophenoldo do Bluish black.

4-sulionic acid.

D0 do 2-anginophenol-4-sulfa- D0.

D0 l.3.5-trihydroxybenzene 4-chloro-2-aminophenoL. Blue-black.

. G-nitro-l.2-aminonaphthol-4- do Anthram'lic acid"; Violettish black.

dyestufis contain in the radicals R and R1 together at most one nitro-group per one chromium atom, being in form of their alkali metal salts dark watersoluble powders dyeing leather fast grey to black shades.

3. The azodyestufis containing chromium in complex union, in the form of its free acid, of the formula:

4. The azodyestuff containing chromium in complex union, in the form of its free acid, of the formula:

H03 NWQOH 0H T dyeing leather grey to black shades.

dyeing leather grey to black shades.

ERNST FELLMER. 

